Genetics of Omega-3 Long-Chain Polyunsaturated Fatty Acid ...
SYNTHESIS AND CHARACTERIZATION OF TRI-, DI-, AND CHLORODIORGANOTIN(IV) DERIVATIVES OF...
17
This article was downloaded by: [Quaid-i-azam University] On: 08 June 2014, At: 23:32 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Synthesis and Reactivity in Inorganic and Metal- Organic Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lsrt19 SYNTHESIS AND CHARACTERIZATION OF TRI-, DI-, AND CHLORODIORGANOTIN(IV) DERIVATIVES OF 3- BENZOYL-α-METHYLPHENYLACETIC ACID AND 3-(2- THIENYL)ACRYLIC ACID Muhammad Tariq Masood a , Saqib Ali b , Muhammad Danish a & Muhammad Mazhar a a Department of Chemistry , Quaid-i-Azam University , 45320 Islamabad, Pakistan b Department of Chemistry , Quaid-i-Azam University , 45320 Islamabad, Pakistan Published online: 15 Feb 2007. To cite this article: Muhammad Tariq Masood , Saqib Ali , Muhammad Danish & Muhammad Mazhar (2002) SYNTHESIS AND CHARACTERIZATION OF TRI-, DI-, AND CHLORODIORGANOTIN(IV) DERIVATIVES OF 3-BENZOYL-α-METHYLPHENYLACETIC ACID AND 3-(2-THIENYL)ACRYLIC ACID, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 32:1, 9-23, DOI: 10.1081/SIM-120013143 To link to this article: http://dx.doi.org/10.1081/SIM-120013143 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Transcript of SYNTHESIS AND CHARACTERIZATION OF TRI-, DI-, AND CHLORODIORGANOTIN(IV) DERIVATIVES OF...
This article was downloaded by [Quaid-i-azam University]On 08 June 2014 At 2332Publisher Taylor amp FrancisInforma Ltd Registered in England and Wales Registered Number 1072954 Registered office MortimerHouse 37-41 Mortimer Street London W1T 3JH UK
Synthesis and Reactivity in Inorganic and Metal-Organic ChemistryPublication details including instructions for authors and subscription informationhttpwwwtandfonlinecomloilsrt19
SYNTHESIS AND CHARACTERIZATION OF TRI- DI-AND CHLORODIORGANOTIN(IV) DERIVATIVES OF 3-BENZOYL-α-METHYLPHENYLACETIC ACID AND 3-(2-THIENYL)ACRYLIC ACIDMuhammad Tariq Masood a Saqib Ali b Muhammad Danish a amp Muhammad Mazhar aa Department of Chemistry Quaid-i-Azam University 45320 Islamabad Pakistanb Department of Chemistry Quaid-i-Azam University 45320 Islamabad PakistanPublished online 15 Feb 2007
To cite this article Muhammad Tariq Masood Saqib Ali Muhammad Danish amp Muhammad Mazhar (2002) SYNTHESIS ANDCHARACTERIZATION OF TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES OF 3-BENZOYL-α-METHYLPHENYLACETICACID AND 3-(2-THIENYL)ACRYLIC ACID Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 321 9-23 DOI101081SIM-120013143
To link to this article httpdxdoiorg101081SIM-120013143
PLEASE SCROLL DOWN FOR ARTICLE
Taylor amp Francis makes every effort to ensure the accuracy of all the information (the ldquoContentrdquo) containedin the publications on our platform However Taylor amp Francis our agents and our licensors make norepresentations or warranties whatsoever as to the accuracy completeness or suitability for any purpose ofthe Content Any opinions and views expressed in this publication are the opinions and views of the authorsand are not the views of or endorsed by Taylor amp Francis The accuracy of the Content should not be reliedupon and should be independently verified with primary sources of information Taylor and Francis shallnot be liable for any losses actions claims proceedings demands costs expenses damages and otherliabilities whatsoever or howsoever caused arising directly or indirectly in connection with in relation to orarising out of the use of the Content
This article may be used for research teaching and private study purposes Any substantial or systematicreproduction redistribution reselling loan sub-licensing systematic supply or distribution in anyform to anyone is expressly forbidden Terms amp Conditions of access and use can be found at httpwwwtandfonlinecompageterms-and-conditions
SYNTHESIS AND CHARACTERIZATION
OF TRI- DI- AND
CHLORODIORGANOTIN(IV)
DERIVATIVES OF 3-BENZOYL-a-METHYLPHENYLACETIC ACID AND
3-(2-THIENYL)ACRYLIC ACID
Muhammad Tariq Masood Saqib Ali Muhammad
Danish and Muhammad Mazhar
Department of Chemistry Quaid-i-Azam University45320 Islamabad Pakistan
ABSTRACT
Various organotin derivatives of 3-benzoyl-a-methylphenyla-cetic acid (HL1) and 3-(2-thienyl)acrylic acid (HL2) of thegeneral formulae R3SnL R2SnL2 and R2Sn(Cl)L whereRfrac14Me Et n-Bu and Ph Lfrac14L1 or L2 have been synthe-sized These compounds were characterized by elementalanalyses infrared mass 1H 13C and 119Sn NMR spectra andthe geometry around the tin atom has been discussed
Corresponding author E-mail drsa54yahoocom
9
Copyright 2002 by Marcel Dekker Inc wwwdekkercom
SYNTH REACT INORG MET-ORG CHEM 32(1) 9ndash23 (2002)
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INTRODUCTION
Since the last two decades173 organotin carboxylates have been se-lected as candidates for the study of their diversified applications and in-teresting structures Their spectroscopic studies show that there are distinctphase-dependent geometries around the tin atom in non-coordinating sol-vents as well as in the solid state477
In continutaion of our previous research work8715 we report here thesynthesis infrared mass and multinuclear (1H 13C 119Sn) NMR spectra ofnew organotin(IV) carboxylates of 3-benzoyl-a-methylphenylacetic acid(HL1) and 3-(2-thienyl)acrylic acid (HL2)
RESULTS AND DISCUSSION
Tri- di- and monochloroorganotin carboxylates of the ligands HL1
and HL2 were prepared by the following general reactions (1)7(3) Theelemental analyses and some of their physical data are given in Table I
R3SnCl thorn AgL1R3SnL1 thorn AgCl
R frac14 Meeth1THORN n-Bueth4THORN and Pheth6THORNeth1THORN
R2SnO thorn 2LHR2SnL2 thorn H2O eth2THORN
L frac14 L1 R frac14 Eteth2THORN n-Bueth3THORN and Pheth5THORNL frac14 L2 R frac14 Eteth7THORN n-Bueth9THORN and Pheth11THORN
R2SnL22 thorn R2SnCl22R2SnethClTHORNL2
R frac14 Eteth8THORN n-Bueth10THORN and Pheth12THORNeth3THORN
Infrared Spectroscopy
In the infrared region the bands of interest are n(COO) n(Sn-C)n(Sn-O) and n(Sn-Cl) as given in Table II A marked shifting is observed inthe COO frequencies for the complexes as compared to the free acid Thisvibration is very important in the prediction of the bonding mode of theligand As shown in Table II the Dn values frac12Dn frac14 nasymethCOOTHORN nsymethCOOTHORN
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Table
IP
hysi
cal
Para
met
ers
an
d119S
nC
hem
ical
Sh
ifts
of
the
Org
an
oti
n(I
V)
Der
ivati
ves
a
Co
mp
ou
nd
(Fo
rmu
laW
eigh
t)G
ener
al
Fo
rmu
laM
elti
ng
Po
int
C
Yie
ld
CC
alc
(F
ou
nd
)
HC
alc
(F
ou
nd
)
119S
np
pm
(1)
C19H
22O
3S
n(4
31)
Me 3
Sn
L1
767
546
8(5
42
0)
52
8(5
30)
1330
(2)
C36H
36O
6S
n(6
83)
Et 2
Sn
L12
770
632
5(6
34
0)
52
7(5
30)
1502
(3)
C40H
40O
6S
n(7
35)
Bu
2S
nl1
27
64
649
5(6
49
0)
59
5(5
85)
1443
(4)
C28H
40O
3S
n(5
43)
Bu
3S
nL
17
70
618
8(6
20
0)
73
7(7
60)
1132
(5)
C44H
36O
6S
n(7
79)
Ph
2S
nL
12
772
676
0(6
78
0)
46
1(4
59)
2023
(6)
C34H
28O
3S
n(6
03)
Ph
3S
nL
17
82
676
6(6
70
0)
46
4(4
60)
1067
(7)
C18H
30O
4S
2S
n(4
93)
Et 2
Sn
L22
997
100
84
447
2(4
50
0)
41
4(4
20)
1578
(8)
C11H
15O
2S
ClS
n(3
655
)E
t 2S
n(C
l)L
27
60
361
1(3
62
0)
41
0(4
12)
980
(9)
C22H
28O
4S
2S
n(5
39)
Bu
2S
nL
22
67ndash68
79
489
7(4
82
0)
52
3(5
26)
1504
(10)
C15H
13O
2S
ClS
n(4
115
)B
u2S
n(C
l)L
27
74
427
0(4
19
0)
54
5(5
50)
330
(11)
C26H
20O
4S
2S
n(5
79)
Ph
2S
nL
22
1017
283
538
8(5
37
2)
34
5(3
48)
2022
(12)
C19H
15O
2S
ClS
n(4
615
)P
h2S
n(C
l)2
769
495
0(4
93
0)
32
5(3
54)
1582
HL
1(C
16H
14O
3)
(254)
94
77
77
HL
2(C
7H
6O
2S
)(1
54)
1457
48
77
77
aC
om
po
un
ds(1
)7(4
)(8
)(1
0)
an
d(1
2)
wer
ese
mis
olid
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 11
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ORDER REPRINTS
are comparable to the values of the silver salts which clearly indicate thebidentate nature of the ligands16 Thus for triorganotin complexes a brid-ging nature is most likely and is further supported by the crystal structure ofthe trimethyl drivative of compound 1
23 In case of the chlorodiorganotinderivatives the presence of a chlorine atom increases the Lewis acidity oftin thus increasing tin-carbonyl interaction which propose the bridging orchelating nature the of ligand However the chelating mode of interaction ismore favourable and is suggested for such compounds17 For the R2SnL2
compounds a bidentate chelate nature of the corboxylate is suggested whichis further suported by the crystal structure24 of the diethyltin derivative ofthe ligand HL2 The bands in the range 6007500 cm1 and 5007400 cm1
indicate Sn-C and Sn-O bonds respectively In the chloro derivatives theSn-Cl band is observed in the region 3577348 cm1 The band position ofthe carbonyl group between two benzene rings of the ligand HL1 is un-affected showing the non-involvment of this group in bonding to tin
Multinuclear NMR
Multinuclear NMR spectra have been carried out in CDCl3 Theexpected resonances were assigned on the basis of their intensity and
Table II Assignments of Characteristic Infrared Vibrations (cm1)
n(COO)
Comp Asym Sym Dn n(Sn-C) n(Sn-O) n(Sn-Cl)
HL1 1677 s 1420 s 257 7 7 7HL2 1688 s 1419 s 269 7 7 7AgL1 1560 s 1390 s 170 7 7 7AgL2 1544 s 1392 s 152 7 7 7(1) 1550 s 1370 s 180 546 m 417 w 7(2) 1560 s 1365 s 195 592 m 438 m 7(3) 1562 s 1370 s 192 548 m 436 m 7(4) 1573 s 1381 s 192 602 s 417 m 7(5) 1553 s 1366 s 187 598 s 480 s 7(6) 1565 s 1382 s 183 602 s 447 w 7(7) 1555 s 1376 s 179 608 m 488 w 7(8) 1552 s 1374 s 178 594 m 448 w 357 s(9) 1563 s 1370 s 193 608 s 488 s 7
(10) 1566 s 1370 s 196 592 m 448 m 348 m
(11) 1572 s 1371 s 201 606 m 482 m 7(12) 1574 s 1374 s 200 590 s 444 m 353 s
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multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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ORDER REPRINTS
Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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ORDER REPRINTS
signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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SYNTHESIS AND CHARACTERIZATION
OF TRI- DI- AND
CHLORODIORGANOTIN(IV)
DERIVATIVES OF 3-BENZOYL-a-METHYLPHENYLACETIC ACID AND
3-(2-THIENYL)ACRYLIC ACID
Muhammad Tariq Masood Saqib Ali Muhammad
Danish and Muhammad Mazhar
Department of Chemistry Quaid-i-Azam University45320 Islamabad Pakistan
ABSTRACT
Various organotin derivatives of 3-benzoyl-a-methylphenyla-cetic acid (HL1) and 3-(2-thienyl)acrylic acid (HL2) of thegeneral formulae R3SnL R2SnL2 and R2Sn(Cl)L whereRfrac14Me Et n-Bu and Ph Lfrac14L1 or L2 have been synthe-sized These compounds were characterized by elementalanalyses infrared mass 1H 13C and 119Sn NMR spectra andthe geometry around the tin atom has been discussed
Corresponding author E-mail drsa54yahoocom
9
Copyright 2002 by Marcel Dekker Inc wwwdekkercom
SYNTH REACT INORG MET-ORG CHEM 32(1) 9ndash23 (2002)
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INTRODUCTION
Since the last two decades173 organotin carboxylates have been se-lected as candidates for the study of their diversified applications and in-teresting structures Their spectroscopic studies show that there are distinctphase-dependent geometries around the tin atom in non-coordinating sol-vents as well as in the solid state477
In continutaion of our previous research work8715 we report here thesynthesis infrared mass and multinuclear (1H 13C 119Sn) NMR spectra ofnew organotin(IV) carboxylates of 3-benzoyl-a-methylphenylacetic acid(HL1) and 3-(2-thienyl)acrylic acid (HL2)
RESULTS AND DISCUSSION
Tri- di- and monochloroorganotin carboxylates of the ligands HL1
and HL2 were prepared by the following general reactions (1)7(3) Theelemental analyses and some of their physical data are given in Table I
R3SnCl thorn AgL1R3SnL1 thorn AgCl
R frac14 Meeth1THORN n-Bueth4THORN and Pheth6THORNeth1THORN
R2SnO thorn 2LHR2SnL2 thorn H2O eth2THORN
L frac14 L1 R frac14 Eteth2THORN n-Bueth3THORN and Pheth5THORNL frac14 L2 R frac14 Eteth7THORN n-Bueth9THORN and Pheth11THORN
R2SnL22 thorn R2SnCl22R2SnethClTHORNL2
R frac14 Eteth8THORN n-Bueth10THORN and Pheth12THORNeth3THORN
Infrared Spectroscopy
In the infrared region the bands of interest are n(COO) n(Sn-C)n(Sn-O) and n(Sn-Cl) as given in Table II A marked shifting is observed inthe COO frequencies for the complexes as compared to the free acid Thisvibration is very important in the prediction of the bonding mode of theligand As shown in Table II the Dn values frac12Dn frac14 nasymethCOOTHORN nsymethCOOTHORN
10 MASOOD ET AL
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Table
IP
hysi
cal
Para
met
ers
an
d119S
nC
hem
ical
Sh
ifts
of
the
Org
an
oti
n(I
V)
Der
ivati
ves
a
Co
mp
ou
nd
(Fo
rmu
laW
eigh
t)G
ener
al
Fo
rmu
laM
elti
ng
Po
int
C
Yie
ld
CC
alc
(F
ou
nd
)
HC
alc
(F
ou
nd
)
119S
np
pm
(1)
C19H
22O
3S
n(4
31)
Me 3
Sn
L1
767
546
8(5
42
0)
52
8(5
30)
1330
(2)
C36H
36O
6S
n(6
83)
Et 2
Sn
L12
770
632
5(6
34
0)
52
7(5
30)
1502
(3)
C40H
40O
6S
n(7
35)
Bu
2S
nl1
27
64
649
5(6
49
0)
59
5(5
85)
1443
(4)
C28H
40O
3S
n(5
43)
Bu
3S
nL
17
70
618
8(6
20
0)
73
7(7
60)
1132
(5)
C44H
36O
6S
n(7
79)
Ph
2S
nL
12
772
676
0(6
78
0)
46
1(4
59)
2023
(6)
C34H
28O
3S
n(6
03)
Ph
3S
nL
17
82
676
6(6
70
0)
46
4(4
60)
1067
(7)
C18H
30O
4S
2S
n(4
93)
Et 2
Sn
L22
997
100
84
447
2(4
50
0)
41
4(4
20)
1578
(8)
C11H
15O
2S
ClS
n(3
655
)E
t 2S
n(C
l)L
27
60
361
1(3
62
0)
41
0(4
12)
980
(9)
C22H
28O
4S
2S
n(5
39)
Bu
2S
nL
22
67ndash68
79
489
7(4
82
0)
52
3(5
26)
1504
(10)
C15H
13O
2S
ClS
n(4
115
)B
u2S
n(C
l)L
27
74
427
0(4
19
0)
54
5(5
50)
330
(11)
C26H
20O
4S
2S
n(5
79)
Ph
2S
nL
22
1017
283
538
8(5
37
2)
34
5(3
48)
2022
(12)
C19H
15O
2S
ClS
n(4
615
)P
h2S
n(C
l)2
769
495
0(4
93
0)
32
5(3
54)
1582
HL
1(C
16H
14O
3)
(254)
94
77
77
HL
2(C
7H
6O
2S
)(1
54)
1457
48
77
77
aC
om
po
un
ds(1
)7(4
)(8
)(1
0)
an
d(1
2)
wer
ese
mis
olid
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 11
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ORDER REPRINTS
are comparable to the values of the silver salts which clearly indicate thebidentate nature of the ligands16 Thus for triorganotin complexes a brid-ging nature is most likely and is further supported by the crystal structure ofthe trimethyl drivative of compound 1
23 In case of the chlorodiorganotinderivatives the presence of a chlorine atom increases the Lewis acidity oftin thus increasing tin-carbonyl interaction which propose the bridging orchelating nature the of ligand However the chelating mode of interaction ismore favourable and is suggested for such compounds17 For the R2SnL2
compounds a bidentate chelate nature of the corboxylate is suggested whichis further suported by the crystal structure24 of the diethyltin derivative ofthe ligand HL2 The bands in the range 6007500 cm1 and 5007400 cm1
indicate Sn-C and Sn-O bonds respectively In the chloro derivatives theSn-Cl band is observed in the region 3577348 cm1 The band position ofthe carbonyl group between two benzene rings of the ligand HL1 is un-affected showing the non-involvment of this group in bonding to tin
Multinuclear NMR
Multinuclear NMR spectra have been carried out in CDCl3 Theexpected resonances were assigned on the basis of their intensity and
Table II Assignments of Characteristic Infrared Vibrations (cm1)
n(COO)
Comp Asym Sym Dn n(Sn-C) n(Sn-O) n(Sn-Cl)
HL1 1677 s 1420 s 257 7 7 7HL2 1688 s 1419 s 269 7 7 7AgL1 1560 s 1390 s 170 7 7 7AgL2 1544 s 1392 s 152 7 7 7(1) 1550 s 1370 s 180 546 m 417 w 7(2) 1560 s 1365 s 195 592 m 438 m 7(3) 1562 s 1370 s 192 548 m 436 m 7(4) 1573 s 1381 s 192 602 s 417 m 7(5) 1553 s 1366 s 187 598 s 480 s 7(6) 1565 s 1382 s 183 602 s 447 w 7(7) 1555 s 1376 s 179 608 m 488 w 7(8) 1552 s 1374 s 178 594 m 448 w 357 s(9) 1563 s 1370 s 193 608 s 488 s 7
(10) 1566 s 1370 s 196 592 m 448 m 348 m
(11) 1572 s 1371 s 201 606 m 482 m 7(12) 1574 s 1374 s 200 590 s 444 m 353 s
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ORDER REPRINTS
multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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INTRODUCTION
Since the last two decades173 organotin carboxylates have been se-lected as candidates for the study of their diversified applications and in-teresting structures Their spectroscopic studies show that there are distinctphase-dependent geometries around the tin atom in non-coordinating sol-vents as well as in the solid state477
In continutaion of our previous research work8715 we report here thesynthesis infrared mass and multinuclear (1H 13C 119Sn) NMR spectra ofnew organotin(IV) carboxylates of 3-benzoyl-a-methylphenylacetic acid(HL1) and 3-(2-thienyl)acrylic acid (HL2)
RESULTS AND DISCUSSION
Tri- di- and monochloroorganotin carboxylates of the ligands HL1
and HL2 were prepared by the following general reactions (1)7(3) Theelemental analyses and some of their physical data are given in Table I
R3SnCl thorn AgL1R3SnL1 thorn AgCl
R frac14 Meeth1THORN n-Bueth4THORN and Pheth6THORNeth1THORN
R2SnO thorn 2LHR2SnL2 thorn H2O eth2THORN
L frac14 L1 R frac14 Eteth2THORN n-Bueth3THORN and Pheth5THORNL frac14 L2 R frac14 Eteth7THORN n-Bueth9THORN and Pheth11THORN
R2SnL22 thorn R2SnCl22R2SnethClTHORNL2
R frac14 Eteth8THORN n-Bueth10THORN and Pheth12THORNeth3THORN
Infrared Spectroscopy
In the infrared region the bands of interest are n(COO) n(Sn-C)n(Sn-O) and n(Sn-Cl) as given in Table II A marked shifting is observed inthe COO frequencies for the complexes as compared to the free acid Thisvibration is very important in the prediction of the bonding mode of theligand As shown in Table II the Dn values frac12Dn frac14 nasymethCOOTHORN nsymethCOOTHORN
10 MASOOD ET AL
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014
ORDER REPRINTS
Table
IP
hysi
cal
Para
met
ers
an
d119S
nC
hem
ical
Sh
ifts
of
the
Org
an
oti
n(I
V)
Der
ivati
ves
a
Co
mp
ou
nd
(Fo
rmu
laW
eigh
t)G
ener
al
Fo
rmu
laM
elti
ng
Po
int
C
Yie
ld
CC
alc
(F
ou
nd
)
HC
alc
(F
ou
nd
)
119S
np
pm
(1)
C19H
22O
3S
n(4
31)
Me 3
Sn
L1
767
546
8(5
42
0)
52
8(5
30)
1330
(2)
C36H
36O
6S
n(6
83)
Et 2
Sn
L12
770
632
5(6
34
0)
52
7(5
30)
1502
(3)
C40H
40O
6S
n(7
35)
Bu
2S
nl1
27
64
649
5(6
49
0)
59
5(5
85)
1443
(4)
C28H
40O
3S
n(5
43)
Bu
3S
nL
17
70
618
8(6
20
0)
73
7(7
60)
1132
(5)
C44H
36O
6S
n(7
79)
Ph
2S
nL
12
772
676
0(6
78
0)
46
1(4
59)
2023
(6)
C34H
28O
3S
n(6
03)
Ph
3S
nL
17
82
676
6(6
70
0)
46
4(4
60)
1067
(7)
C18H
30O
4S
2S
n(4
93)
Et 2
Sn
L22
997
100
84
447
2(4
50
0)
41
4(4
20)
1578
(8)
C11H
15O
2S
ClS
n(3
655
)E
t 2S
n(C
l)L
27
60
361
1(3
62
0)
41
0(4
12)
980
(9)
C22H
28O
4S
2S
n(5
39)
Bu
2S
nL
22
67ndash68
79
489
7(4
82
0)
52
3(5
26)
1504
(10)
C15H
13O
2S
ClS
n(4
115
)B
u2S
n(C
l)L
27
74
427
0(4
19
0)
54
5(5
50)
330
(11)
C26H
20O
4S
2S
n(5
79)
Ph
2S
nL
22
1017
283
538
8(5
37
2)
34
5(3
48)
2022
(12)
C19H
15O
2S
ClS
n(4
615
)P
h2S
n(C
l)2
769
495
0(4
93
0)
32
5(3
54)
1582
HL
1(C
16H
14O
3)
(254)
94
77
77
HL
2(C
7H
6O
2S
)(1
54)
1457
48
77
77
aC
om
po
un
ds(1
)7(4
)(8
)(1
0)
an
d(1
2)
wer
ese
mis
olid
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 11
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ORDER REPRINTS
are comparable to the values of the silver salts which clearly indicate thebidentate nature of the ligands16 Thus for triorganotin complexes a brid-ging nature is most likely and is further supported by the crystal structure ofthe trimethyl drivative of compound 1
23 In case of the chlorodiorganotinderivatives the presence of a chlorine atom increases the Lewis acidity oftin thus increasing tin-carbonyl interaction which propose the bridging orchelating nature the of ligand However the chelating mode of interaction ismore favourable and is suggested for such compounds17 For the R2SnL2
compounds a bidentate chelate nature of the corboxylate is suggested whichis further suported by the crystal structure24 of the diethyltin derivative ofthe ligand HL2 The bands in the range 6007500 cm1 and 5007400 cm1
indicate Sn-C and Sn-O bonds respectively In the chloro derivatives theSn-Cl band is observed in the region 3577348 cm1 The band position ofthe carbonyl group between two benzene rings of the ligand HL1 is un-affected showing the non-involvment of this group in bonding to tin
Multinuclear NMR
Multinuclear NMR spectra have been carried out in CDCl3 Theexpected resonances were assigned on the basis of their intensity and
Table II Assignments of Characteristic Infrared Vibrations (cm1)
n(COO)
Comp Asym Sym Dn n(Sn-C) n(Sn-O) n(Sn-Cl)
HL1 1677 s 1420 s 257 7 7 7HL2 1688 s 1419 s 269 7 7 7AgL1 1560 s 1390 s 170 7 7 7AgL2 1544 s 1392 s 152 7 7 7(1) 1550 s 1370 s 180 546 m 417 w 7(2) 1560 s 1365 s 195 592 m 438 m 7(3) 1562 s 1370 s 192 548 m 436 m 7(4) 1573 s 1381 s 192 602 s 417 m 7(5) 1553 s 1366 s 187 598 s 480 s 7(6) 1565 s 1382 s 183 602 s 447 w 7(7) 1555 s 1376 s 179 608 m 488 w 7(8) 1552 s 1374 s 178 594 m 448 w 357 s(9) 1563 s 1370 s 193 608 s 488 s 7
(10) 1566 s 1370 s 196 592 m 448 m 348 m
(11) 1572 s 1371 s 201 606 m 482 m 7(12) 1574 s 1374 s 200 590 s 444 m 353 s
12 MASOOD ET AL
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ORDER REPRINTS
multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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ORDER REPRINTS
Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
14 MASOOD ET AL
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] at
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32 0
8 Ju
ne 2
014
ORDER REPRINTS
Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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ORDER REPRINTS
Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
16 MASOOD ET AL
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ORDER REPRINTS
signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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ORDER REPRINTS
Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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ORDER REPRINTS
Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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ORDER REPRINTS
vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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ORDER REPRINTS
Table
IP
hysi
cal
Para
met
ers
an
d119S
nC
hem
ical
Sh
ifts
of
the
Org
an
oti
n(I
V)
Der
ivati
ves
a
Co
mp
ou
nd
(Fo
rmu
laW
eigh
t)G
ener
al
Fo
rmu
laM
elti
ng
Po
int
C
Yie
ld
CC
alc
(F
ou
nd
)
HC
alc
(F
ou
nd
)
119S
np
pm
(1)
C19H
22O
3S
n(4
31)
Me 3
Sn
L1
767
546
8(5
42
0)
52
8(5
30)
1330
(2)
C36H
36O
6S
n(6
83)
Et 2
Sn
L12
770
632
5(6
34
0)
52
7(5
30)
1502
(3)
C40H
40O
6S
n(7
35)
Bu
2S
nl1
27
64
649
5(6
49
0)
59
5(5
85)
1443
(4)
C28H
40O
3S
n(5
43)
Bu
3S
nL
17
70
618
8(6
20
0)
73
7(7
60)
1132
(5)
C44H
36O
6S
n(7
79)
Ph
2S
nL
12
772
676
0(6
78
0)
46
1(4
59)
2023
(6)
C34H
28O
3S
n(6
03)
Ph
3S
nL
17
82
676
6(6
70
0)
46
4(4
60)
1067
(7)
C18H
30O
4S
2S
n(4
93)
Et 2
Sn
L22
997
100
84
447
2(4
50
0)
41
4(4
20)
1578
(8)
C11H
15O
2S
ClS
n(3
655
)E
t 2S
n(C
l)L
27
60
361
1(3
62
0)
41
0(4
12)
980
(9)
C22H
28O
4S
2S
n(5
39)
Bu
2S
nL
22
67ndash68
79
489
7(4
82
0)
52
3(5
26)
1504
(10)
C15H
13O
2S
ClS
n(4
115
)B
u2S
n(C
l)L
27
74
427
0(4
19
0)
54
5(5
50)
330
(11)
C26H
20O
4S
2S
n(5
79)
Ph
2S
nL
22
1017
283
538
8(5
37
2)
34
5(3
48)
2022
(12)
C19H
15O
2S
ClS
n(4
615
)P
h2S
n(C
l)2
769
495
0(4
93
0)
32
5(3
54)
1582
HL
1(C
16H
14O
3)
(254)
94
77
77
HL
2(C
7H
6O
2S
)(1
54)
1457
48
77
77
aC
om
po
un
ds(1
)7(4
)(8
)(1
0)
an
d(1
2)
wer
ese
mis
olid
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 11
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ORDER REPRINTS
are comparable to the values of the silver salts which clearly indicate thebidentate nature of the ligands16 Thus for triorganotin complexes a brid-ging nature is most likely and is further supported by the crystal structure ofthe trimethyl drivative of compound 1
23 In case of the chlorodiorganotinderivatives the presence of a chlorine atom increases the Lewis acidity oftin thus increasing tin-carbonyl interaction which propose the bridging orchelating nature the of ligand However the chelating mode of interaction ismore favourable and is suggested for such compounds17 For the R2SnL2
compounds a bidentate chelate nature of the corboxylate is suggested whichis further suported by the crystal structure24 of the diethyltin derivative ofthe ligand HL2 The bands in the range 6007500 cm1 and 5007400 cm1
indicate Sn-C and Sn-O bonds respectively In the chloro derivatives theSn-Cl band is observed in the region 3577348 cm1 The band position ofthe carbonyl group between two benzene rings of the ligand HL1 is un-affected showing the non-involvment of this group in bonding to tin
Multinuclear NMR
Multinuclear NMR spectra have been carried out in CDCl3 Theexpected resonances were assigned on the basis of their intensity and
Table II Assignments of Characteristic Infrared Vibrations (cm1)
n(COO)
Comp Asym Sym Dn n(Sn-C) n(Sn-O) n(Sn-Cl)
HL1 1677 s 1420 s 257 7 7 7HL2 1688 s 1419 s 269 7 7 7AgL1 1560 s 1390 s 170 7 7 7AgL2 1544 s 1392 s 152 7 7 7(1) 1550 s 1370 s 180 546 m 417 w 7(2) 1560 s 1365 s 195 592 m 438 m 7(3) 1562 s 1370 s 192 548 m 436 m 7(4) 1573 s 1381 s 192 602 s 417 m 7(5) 1553 s 1366 s 187 598 s 480 s 7(6) 1565 s 1382 s 183 602 s 447 w 7(7) 1555 s 1376 s 179 608 m 488 w 7(8) 1552 s 1374 s 178 594 m 448 w 357 s(9) 1563 s 1370 s 193 608 s 488 s 7
(10) 1566 s 1370 s 196 592 m 448 m 348 m
(11) 1572 s 1371 s 201 606 m 482 m 7(12) 1574 s 1374 s 200 590 s 444 m 353 s
12 MASOOD ET AL
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ORDER REPRINTS
multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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ORDER REPRINTS
Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
14 MASOOD ET AL
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ORDER REPRINTS
Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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ORDER REPRINTS
Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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are comparable to the values of the silver salts which clearly indicate thebidentate nature of the ligands16 Thus for triorganotin complexes a brid-ging nature is most likely and is further supported by the crystal structure ofthe trimethyl drivative of compound 1
23 In case of the chlorodiorganotinderivatives the presence of a chlorine atom increases the Lewis acidity oftin thus increasing tin-carbonyl interaction which propose the bridging orchelating nature the of ligand However the chelating mode of interaction ismore favourable and is suggested for such compounds17 For the R2SnL2
compounds a bidentate chelate nature of the corboxylate is suggested whichis further suported by the crystal structure24 of the diethyltin derivative ofthe ligand HL2 The bands in the range 6007500 cm1 and 5007400 cm1
indicate Sn-C and Sn-O bonds respectively In the chloro derivatives theSn-Cl band is observed in the region 3577348 cm1 The band position ofthe carbonyl group between two benzene rings of the ligand HL1 is un-affected showing the non-involvment of this group in bonding to tin
Multinuclear NMR
Multinuclear NMR spectra have been carried out in CDCl3 Theexpected resonances were assigned on the basis of their intensity and
Table II Assignments of Characteristic Infrared Vibrations (cm1)
n(COO)
Comp Asym Sym Dn n(Sn-C) n(Sn-O) n(Sn-Cl)
HL1 1677 s 1420 s 257 7 7 7HL2 1688 s 1419 s 269 7 7 7AgL1 1560 s 1390 s 170 7 7 7AgL2 1544 s 1392 s 152 7 7 7(1) 1550 s 1370 s 180 546 m 417 w 7(2) 1560 s 1365 s 195 592 m 438 m 7(3) 1562 s 1370 s 192 548 m 436 m 7(4) 1573 s 1381 s 192 602 s 417 m 7(5) 1553 s 1366 s 187 598 s 480 s 7(6) 1565 s 1382 s 183 602 s 447 w 7(7) 1555 s 1376 s 179 608 m 488 w 7(8) 1552 s 1374 s 178 594 m 448 w 357 s(9) 1563 s 1370 s 193 608 s 488 s 7
(10) 1566 s 1370 s 196 592 m 448 m 348 m
(11) 1572 s 1371 s 201 606 m 482 m 7(12) 1574 s 1374 s 200 590 s 444 m 353 s
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multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
16 MASOOD ET AL
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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ORDER REPRINTS
Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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ORDER REPRINTS
Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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ORDER REPRINTS
vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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ORDER REPRINTS
Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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ORDER REPRINTS
8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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ORDER REPRINTS
multiplicity pattern as well as their coupling constants The peak integra-tions of the spectra are in accordance with the number of protons proposedfor each fragment of the molecule The numbering scheme for ligands isgiven in Fig 1 The aromatic carbon resonances were assigned by com-paring experimental chemical shifts with those calculated by the incrementalmethod18a and literature values18b
In triorganotin carboxylates 1J[119Sn-13C] the indirect tin protoncoupling constants 2J[119Sn-1H] and 119Sn chemical shifts (Tables I III7VI)describe a tetrahedral geometry around the tin atom1920
For trimethyltin 3-benzoyl-a-methylphenylacete 1J[119Sn-13C] and2J[119Sn-1H] are 400 and 582 Hz respectively Using Lockhartrsquos andHolecekrsquos relations2122 the C-Sn-C bond angle calculated for this com-pound is 111 However this angle is a little bit less than the C-Sn-C bondangle obtained from the crystal structure of this compound23 This showsthat there are two distinct phase-dependent geometries around the tin atomin such compounds Therefore the average C-Sn-C angle (111) suggests amonomeric tetrahedral environment around the tin atom in non-co-ordinating solvents In the solid phase however such compounds have adistorted trigonal bipyramidal geometry with a polymeric structure823 It istherefore suggested that all of the triorganotin derivatives are monomeric innon-coordinating solvents with tetrahedral geometry (Fig 2(a)) and arepolymeric in the solid state (Fig 2(b))
Unlike triorganotin carboxylates in solution the geometry of dior-ganotin carboxylates cannot be defined with certainty because of dynamicprocesses involving the carboxylate oxygens due to competition in theircoordination behaviour with the tin atom9 However in the solid state thetin atom is hexa-coordinated in such systems24 (Fig 2(c))
In chlorodiorganotin carboxylates 1J[119Sn-13C] and 2J[119Sn-1H]could only be resolved for Et2Sn(Cl)L (Tables V and VI) due to very broad
Figure 1 Structures of the ligands
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 13
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Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
14 MASOOD ET AL
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ORDER REPRINTS
Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Table
III
1H
NM
RD
ata
ab
co
fT
ri-
an
dD
iorg
an
oti
nC
arb
oxyly
tes
of
HL
1
Co
mp
ou
nd
Pro
ton
(1)
Rfrac14
Me
(2)
Rfrac14
Et
(3)
Rfrac14n-B
u(4
)Rfrac14n-B
u(5
)Rfrac14
Ph
(6)
Rfrac14
Ph
277
6(s
)77
4(s
)77
3(s
)77
6(s
)77
5(s
)77
4(s
)4
74
0(d
75
)76
6(d
76
)76
5(d
80
)76
0(d
75
)76
7(d
78
)76
7(d
75
)
573
8(t
76
)74
1(t
70
)74
0(t
77
)73
5(t
76
)74
2(t
75
)74
0(t
75
)6
74
0(d
75
)74
4(d
75
)74
0(d
75
)74
0(d
80
)74
4(d
78
)75
0(d
80
)91
377
7(d
73
)78
5(d
75
)77
6(d
74
)77
4(d
74
)78
3(d
73
)77
8(d
74
)101
276
3(d
73
)75
5(d
72
)75
3(d
69
)75
5(d
71
)75
3(d
71
)75
3(d
71
)
11
75
4(d
d
72
58
)76
4(d
d
72
61
)76
3(d
d
72
60
)76
2(d
d
72
57
)76
5(d
d
70
76
)76
7(d
d
73
58
)14
37
6(q
78
)38
6(q
78
)38
2(q
78
)37
5(q
78
)38
2(q
78
)39
1(q
78
)16
14
7(d
70
)11
4(d
72
)15
1(d
70
)14
8(d
70
)15
0(d
70
)15
6(d
70
)
a05
2J[
57]
15
4(m
)2J[
68]
14
9ndash16
2(m
)14
8ndash15
8(m
)7
7b
715
03J[
140]
11
9ndash13
2(m
)14
2ndash14
7(m
)77
6ndash77
7(m
)77
4ndash77
6(m
)g
77
11
9ndash13
2(m
)14
2ndash14
7(m
)77
1ndash7ndash74
(m)
77
0ndash77
4(m
)
d7
711
2(t
)12
2(t
)77
5ndash77
6(m
)75
4ndash75
5(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zbM
ult
iplici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
14 MASOOD ET AL
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Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Table IV 13C NMR Dataabc of Tri- and Diorganotin Carboxylates of HL1
Compound
Carbon(1)
Rfrac14Me
(2)
Rfrac14Et
(3)
Rfrac14 n-Bu
(4)
Rfrac14 n-Bu
(5)
Rfrac14Ph
(6)
Rfrac14Ph
1 1324 1324 1323 1323 1326 13532 1300 1300 1300 1300 1317 1315
3 1430 1410 1424 1424 1401 14154 1286 1290 1285 1285 1316 12895 1284 1285 1282 1282 1286 1280
6 1324 1324 1323 1316 1326 13227 1966 1965 1964 1966 1960 19638 1380 1378 1379 1376 1374 1366
913 1292 1291 1293 1293 1293 12931012 1283 1283 1282 1283 1283 128311 1316 1315 1316 1318 1286 1292
14 297 297 268 269 297 29615 1790 1843 1791 1791 1805 180216 194 188 191 193 181 190a 23
1J[400]
1751J[600]
29661J[560]
17521J[370]
13751J[640]
13801J[650]
b 7 872J[435]
27752J[34]
19122J[25]
13652J[50]
13602J[50]
g 7 7 1903J[96]
1653J[no]
12853J[69]
12803J[no]
d 7 7 1354J[no]
1364J[no]
13104J[32]
13004J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 15
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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ORDER REPRINTS
signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Table
V
1H
NM
RD
ata
ab
co
fD
i-an
dC
hlo
rod
iorg
an
oti
nC
arb
oxyla
tes
of
HL
2
Co
mp
ou
nd
P
roto
n
(7)
Rfrac14
Et
(8)
Rfrac14
Et
(9)
Rfrac14n-B
u
(10)
Rfrac14n-B
u
(11)
Rfrac14
Ph
(12)
Rfrac14
Ph
376
(d
75
)73
1(d
76
)73
7(d
74
)73
3(d
75
)73
5(d
75
)73
4(d
75
)
470
3(d
d
41
)70
6(d
d
73
)70
5(d
d
42
)70
5(d
d
73
)72
3(d
d
42
)70
4(d
d
73
)5
72
2(d
38
)72
7(d
29
)72
3(d
29
)62
6(d
29
)72
3(d
29
)72
8(d
29
)6
62
5(d
155
)62
4(d
157
)62
7(d
157
)62
3(d
157
)62
8(d
157
)62
4(d
158
)7
78
5(d
155
)78
6(d
157
)78
6(d
157
)78
8(d
157
)78
6(d
157
)78
7(d
158
)
a18
8(m
)2J[
71]
18
0(m
)2J[
64]
17
0(m
)17
0717
3(m
)7
7b
13
2(t
)3J[
140]
12
8(t
)3J[
125]
13
5ndash14
0(m
)13
6ndash14
0(m
)77
3ndash77
5(m
)77
5ndash77
7(m
)g
77
13
5ndash14
0(m
)13
6ndash14
0(m
)77
6ndash77
9(m
)76
0ndash76
2(m
)
d7
709
5(t
)09
2(t
)75
5ndash75
7(m
)76
4ndash76
6(m
)
aC
hem
ical
shif
ts(d
)in
pp
m
nJ(
1H
-1H
)an
dnJ[
119S
n-1
H]
inH
zb
Mu
ltip
lici
tyis
giv
enb
ysfrac14
sin
gle
tdfrac14
do
ub
let
tfrac14
trip
let
an
dmfrac14
mu
ltip
let
c
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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signals in the 13C and 1H spectra The high electronegativity of tin due to thepresence of chloride ion increases the magnitude of the 1J[119Sn-13C] and2J[119Sn-1H] coupling constants25 In our compounds the presence of oxy-gen and chlorine atoms attached to tin increases its Lewis acidity and fa-cilitates chelation of the carbonyl oxygen resulting in a trigonal bipyramidalgeometry Hence comparison of these coupling constants and tin chemicalshifts with previous data suggests a penta-coordinated state for the tinatom915 (Fig 2(d))
Table VI 13C NMR Dataabc of Di- and Chlorodiorganotin Carboxylates of HL2
Compound
Carbon(7)
Rfrac14Et(8)
Rfrac14Et(9)
Rfrac14 n-Bu(10)
Rfrac14 n-Bu(11)
Rfrac14Ph(12)
Rfrac14Ph
2 1386 1340 1385 1330 1386 13303 1290 1300 1286 1292 1289 12904 1279 1287 1279 1280 1280 1280
5 1308 1312 1308 1304 1307 13006 1394 1400 1394 1396 1394 13907 1163 1154 1164 1152 1165 1150
8 1758 1760 1758 1756 1758 1760a 176
1J[605]179
1J[530]250
1J[560]262
1J[502]1376
1J[620]1372
1J[650]b 88
2J[42]
912J[40]
2652J[33]
2662J[35]
13402J[48]
13522J[50]
g 7 7 2623J[90]
2623J[93]
13483J[70]
12783J[69]
d 7 7 1344J[no]
1344J[no]
13004J[34]
13104J[no]
aChemical shifts (d) in ppm nJ(1H-1H) and nJ[119Sn-1H] in Hzbnofrac14 not observedc
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 17
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Mass Spectrometry
The mass fragmentation data of both series are given in Tables VII-IXThe molecular ion peaks as reported earlier914 are not observed for mostof the compounds Generally in triorganotin derivatives the major frag-mentation is the loss of an R group followed by the elimination of CO2 Analternate route of ragmentation is the loss of ligand anion first followed bythe loss of successive R groups until Snthorn is obtained For diorganotin di-carboxylates the main fragmentation is due to the loss of one ligand whichfollows the loss of CO2 and then successive losses of two R groups Chloroderivatives follow the same pattern as the triorganotin carboxylates Thefirst loss is due to an R group followed by CO2 and then another R groupand some fragments of the ligand
EXPERIMENTAL
Instrumentation
Melting points were determined in a capillary tube using an electro-thermal melting point apparatus Model MP-D Mitamura Rikero Kogyo(Japan) and are uncorrected Infrared spectra were recorded in KBr pelletsusing a Hitachi Model 270-50 infrared spectrophotometer The NMRspectra were recorded on Bruker 250ARX spectrometer in CDCl3 usingMe4Si as reference for 1H and 13C and Me4Sn as reference for 119Sn
Figure 2 Suggested structures of the complexes
18 MASOOD ET AL
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ORDER REPRINTS
Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Synthesis
Triorganotin Carboxylates (Compounds (1) (4) and (6))
Compounds with the general formula R3SnL1 were prepared by doubledisplacement reaction between AgL1 and R3SnCl [eq (1)]1314 The silver salt ofthe ligand AgL1 (368 g 001 mole) was suspended in 50 mL dry chloroform ina 250 mL two-necked round bottom flask equipped with a water-cooledcondenser and a magnetic stirrer The appropriate triorganotin chloride(001 mole) in 50 mL dry chloroform was added dropwise to the suspensionwith constant stirring The reaction mixture was then refluxed for 678 hourscooled to room temperature and allowed to stand overnight at room tem-perature AgCl formed during the reaction was filtered off using a conven-tional Schlenk apparatus The filtrate was treated with activated charcoal at50 C filtered and the solvent was removed under reduced pressure The solidmass obtained was crystallized from a suitable solvent (dichloromethane or n-hexane) Physical parameters of these compounds are given in Table I
Diorganotin Carboxylates (Compounds (2) (3) (5) (7) (9) and (11))
Diorganotin compounds were prepared by the condensation reactionof the ligand acids HL and organotin oxide [eq (2)]14 The ligand acid HL1
(522 g) or HL2 (722 g 002 mole) and the appropriate organotin oxide(001 mole) were refluxed in 100 mL dry toluene for 476 hours Waterformed during the reaction was continuously removed using a Dean-Starkapparatus Toluene was then removed under reduced pressure with a high
Table VII Fragmentation Pattern and Relative Abundance () of TriorganotinCarboxylates of HL1
Fragment ion (1) Rfrac14Me (4) Rfrac14 n-Bu (6) Rfrac14Ph
[R3SnO2CR0]thorn 7 7 4
[R2SnO2CR0]thorn 10 56 8[R3SnR0]thorn 51 8 38[RSnR0]thorn 7 21 7[R3Sn]thorn 100 67 96[R2Sn]thorn 7 7 14[RSn]thorn 40 38 66
[HO2CR0]thorn 30 27 12[SnO2CR0]thorn 40 6 21[C7H5O] 37 84 100
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 19
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ORDER REPRINTS
vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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ORDER REPRINTS
Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Qua
id-i
-aza
m U
nive
rsity
] at
23
32 0
8 Ju
ne 2
014
ORDER REPRINTS
vacuum pump The residue was treated with activated charcoal in 150 mLdry chloroform and filtered The filtrate was concentrated and left overnightat 5 C The semisolidsolid mass was crystallized or extracted by usingappropriate solvents (dichloromethane chloroform or n-hexane) Physicalparameters are given in Table I
Table VIII Fragmentation Pattern and Relative Abundance () of DiorganotinCarboxylates of HL1 and HL2
Fragment ion(2)
Rfrac14Et(3)
Rfrac14 n-Bu(5)
Rfrac14Ph(7)
Rfrac14Et(9)
Rfrac14 n-Bu(11)
Rfrac14Ph
[R2Sn(O2CR0)2]thorn
[RSn(O2CR0)2]thorn 68 42 22 85 84 30
[RSn(O2CR0)R0]thorn 58 16 18 61 27 16
[RSnR02]thorn 10 20 11 49 5 12
[R2SnO2CR0]thorn 38 60 8 14 11 31[R2SnR0]thorn 16 8 28 12 2 24
[SnR0]thorn 6 10 63 65 9[HO2CR0]thorn 18 22 6 79 5 74[R2SnO]thorn 70 68 64 [C7H5O]thorn 100 84 82 [SnOH] 100 100 76[C2H5S] 82 69 20[C5H5] 67 40 76
Table IX Fragmentation Pattern and Relative Abundance () of Mono-chlorodiorganotin Carboxylates of HL2
Fragmentation ion (8) Rfrac14Et (10) Rfrac14 n-Bu (12) Rfrac14Ph
[R2Sn(O2CR0)(Cl)]thorn 7 7 7[RSn(O2CR0)(Cl)]thorn 16 7 100[RSn(R0)(Cl)]thorn 5 7 7[SnR0(Cl)]thorn 4 3 8[R2Sn(O2CR0)]thorn 2 9 76[R2Sn(Cl)]thorn 3 6 8
[SnR0]thorn 26 35 28[HO2CR0]thorn 22 78 31[C4H3SSn]thorn 7 9 6
[Sn-OH]thorn 100 100 65[C5H5]
thorn 39 21 7
20 MASOOD ET AL
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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ORDER REPRINTS
8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Chlorodiorganotin Carboxylates (Compounds (8) (10) and (12))
These compounds were prepared according to our previously reportedmethod [eq (3)]15 Equimolar amounts (100 mmol) of R2SnL2 and R2SnCl2were refluxed in 100 mL dry chloroform for 678 hours The reaction mixturewas then concentrated under vacuum and kept at 10 C for 10715 daysThe semisolid or solid mass thus obtained was purified by repeated ex-traction with an appropriate solvents mixture (dichloromethanen-hexane11) Physical parameters are given in Table I
ACKNOWLEDGMENTS
Financial support for this work from Quaid-I-Azam University ishighly acknowledged We are thankful to Rhone-Poulenc for providing theligand 3-benzoyl-a-methylphenylacetic acid
REFERENCES
1 Holmes RR Schmid CG Chandrasekhar V Day RO HolmesJM Oxo Carboxylate Tin Ladder Cluster A New Structural Class ofOrganotin Compounds J Am Chem Soc 1987 109 140871414
2 Valles PG Peruzzo V Tagliavini V Ganis P The Crystal Structureof Di-m-3-oxo-bis(m-monochloroacetato-OO0)bis(monochloroacetato)-tetra-kis[dimethyltin(IV)] J Organomet Chem 1984 276 32579
3 Tiekink ERT Structural Chemistry of Organotin CarboxylatesA Review of the Crystallographic Literature Appl OrganometChem 1991 5 1723
4 Danish M Alt HG Badshah A Ali S Mazhar M Islam NOrganotin Esters of 3-(2-Furanyl)-2-propenoic Acid Their Character-ization and Biological Activity J Organomet Chem 1995 486 51756
5 Sandhu SK Hundal R Tiekink ERT Structural Chemistry ofOrganotin Carboxylates XVII Diorganotin(IV) Derivatives of N-Phthaloyl-DL-Valine J Organomet Chem 1992 430 15723
6 Badshah A Danish M Ali S Mazhar M Mahmood S Synthesisand Characterization of Di- and Triorganotin(IV) Compounds of 3-(2-Thienyl)-2-propenoic Acid Synth React Inorg Met-Org Chem1994 24 115571166
7 Danish M Ali S Mazhar M Badshah A Masood T TiekinkERT Crystal and Molecular Structures of Two Polymeric Triorga-notin 3-(2-Thienyl)-2-propenoate Derivatives Main Group MetChem 1995 18 27734
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 21
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8 Ju
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014
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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ded
by [
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id-i
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m U
nive
rsity
] at
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ne 2
014
ORDER REPRINTS
Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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rsity
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ne 2
014
Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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8 Danish M Ali S Mazhar M Badshah A Tiekink ERT Crystaland Molecular Structures of Bis[(3-(2-furanyl)-2-propenoate)di-N-bu-tyltin]oxide and Triphenyltin 3-(2-Furanyl)-2-propenoate MainGroup Met Chem 1995 18 6977705
9 Danish M Ali S Mazhar M Badshah A Chaudhary MIAlt HG Kehr G Mossbauer Multinuclear Magnetic Resonanceand Mass Spectrometric Studies of Organotin Carboxylates of m-Methyl-trans-cinnamic Acid Polyhedron 1995 14 311573123
10 Danish M Ali S Mazhar M Badshah A Synthesis and SpectralStudies of Bisdialkyl[trans-3-(2-thiophenyl)-2-propenoate]tinoxideCrystal Structure of [(CH3)2SnO2C-CHfrac14CH-C4H3S]O2 MainGroup Met Chem 1996 19 1217131
11 Danish M Badshah A Ali S Mazhar M Islam N ChaudharyMI Preparation and NMR Mass and Mossbauer Studies of Di- andTriorganotin(IV) Derivatives of 3-(2-Furanyl)-2-propenoic Acid IranJ Chem amp Chem Eng 1994 13 176 Chem Abstr 1995 123 56081
12 Danish M Ali S Badshah A Mazhar M Massod H Malik AKehr G 1H 13C 119Sn NMR 119mSn Mossbauer Infrared and MassSpectrometric Studies of Organotin Carboxylates of 2-[(23-Di-methylphenyl)amino]-benzoic Acid Their Effect on MicroorganismSynth React Inorg Met-Org Chem 1997 7 8637885
13 Ali S Danish M Badshah A Mazhar M Rehman A Islam NSynthesis Characterization and Biological Activity of Organotin De-rivatives of 3-(2-Furanyl)-2-propenoic Acid and 3-(2-Thienyl)-2-pro-penoic Acid J Chem Soc Pak 1993 15 1547156
14 Gielen M El Khloufi A Biesemans M Kayser F Willem RDiorganotin 2-Fluorocinnamates and 4-Fluorophenylacetates Synth-esis Characterization and in vitro Antitumor Activity Appl Orga-nomet Chem 1993 7 20176
15 Ali S Danish M Mazhar M Redistribution Reactions of Dior-ganotindicarboxylates and Diorganotindihalides A ConvenientMethod for the Preparation of Halo-diorganotincarboxylates Het-eroatom Chem 1997 3 2737278
16 Wrackmeyer B Vollrath H Ali S Spirocyclic Stannole Derivativesby 11-Organoboration of 22-Bis(1-alkynyl)-13-di-tert-butyl-132-diaza-stannacyclohexanes Inorg Chim Acta 1999 296 26732
17 (a) Molloy KC Quill K Nowell IW Organotin Biocides Part 8The Crystal Structure of Triphenyltin Formate and ComparativeVariable-temperature Tin-119 Mossbauer Spectroscopic Study of Or-ganotin Formate and Acetates J Chem Soc Dalton Trans 19871017106 (b) Molloy KC Biorganotin Compounds in Hartley FR
22 MASOOD ET AL
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ded
by [
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id-i
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nive
rsity
] at
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014
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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ne 2
014
Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Ed The Chemistry of the Metal-Carbon Bond John Willey NewYork 1989 5 465
18 (a) Kalinowski HO Berger S Brown S 13C NMR SpecktrosckopieThieme Verlag Stuttgart Germany 1984 (b) Ballico E Floris BMetalation of Alkynes Part 9 Substituent Effect in Acetox-ymercuration of Arylphenylethynes Main Group Met Chem 199821 5277542
19 Dolling K Krug A Hartung H Weichman H C-Stannylmethy-lated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives ZAnorg Allg Chem 1995 621 63771
20 Wrackmeyer B Kehr G Sub J 11-Organoboration of Di-1-alky-nylsilanes with Alkynyl Groups of Different Reactivity New Orga-nometallis-Substituted Siloles Chem Ber 1993 126 222176
21 Lockhart TP Menders WF Holt EM Solution and Solid-stateMolecular Structures of Me2Sn(OAc)2 and its Hydrolyzate ([Me2-Sn(OAc)]2O)2 by Solution and Solid-state Carbon-13 NMR X-RayDifffraction Study of the Hydrolyzate J Am Chem Soc 1986 1086611716
22 (a) Holecek J Lycka A Dependence of [1J(tin-119-carbon-13)] onthe Carbon-Tin-Carbon Angle in Butyltin(IV) Compounds InorgChim Acta 1986 118 L157L16 (b) Holecek J Handller K Nad-vornik M Lycka A Dependence of [1J(tin-119-carbon-13)] on theMean Carbon-Tin-Carbon Angle in Phenyltin(IV) Compounds ZChem 1990 30 26576
23 Tahir MN Ulku D Ali S Masood M T Danish MMazhar M (Ketoprofenato)trimethyltin(IV) Acta Cryst 1997 C53157471576
24 Parvez M Ali S Masood M T Mazhar M Danish M DiethylBis[3-(2-thiophenyl)-2-propenoate-OO0]tin(IV) Acta Cryst 1997C53 121171213
25 Wrackmeyer B Kehr G Tetra-1-alkynyltin Compounds and Ex-change Reactions with Tin Tetrachloride 13C and 119Sn NuclearMagnetic Resonance Study Main Group Met Chem 1993 16305714
Received January 5 2000Accepted September 23 2001
Referee I K MoedritzerReferee II M K Denk
TRI- DI- AND CHLORODIORGANOTIN(IV) DERIVATIVES 23
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32 0
8 Ju
ne 2
014
Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Order now
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081SIM120013143
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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![N-[4-(3-methyl-3-mesityl-cyclobutyl)-thiazol-2-yl]-succinamic acid: X-ray structure, spectroscopic characterization and quantum chemical computational studies](https://static.fdokumen.com/doc/165x107/632d25baa00d0388c2095a8a/n-4-3-methyl-3-mesityl-cyclobutyl-thiazol-2-yl-succinamic-acid-x-ray-structure.jpg)
